N, n-dinitro dicarbamates



United States Patent 2,978,490 N,N-DINITRO DICARBAMATES Milton B.Frankel, Pasadena, Calif., assignor to Aeroiet General Corporation,Azusa, Calif., a corporation of Ohio No Drawing. Filed Jan. 3, 1955,Ser. .No. 479,657 18 Claims. (Cl. 260-482) This invention relates to newcompositions of matter and a method for their preparation. Inparticular, it

relates to N,N'-dinitro dicarbamates having the general formula:

NO; 0 0 N0 wherein R, R, and A are as defined above.

acetic anhydride was added to 10 ml. of 100% nitric acid.N,N-bis(3,3-dinitrobutyl)-2,2-dinitropropylene di- 1 carbamate was addedportionwise to the solution; The

solution was then stirred for 20 minutes at -10 C. and then poured overice. The resulting white solid-was washed with water and recrystallizedfrom ethylene dichloride in 88% yield, M.P. 117118 C. The elementalanalysis of the product isas follows:

Calculated for C H N O percent C, 24.61; percent 1 H, 2.86; percent N,22.08. Found: percent C, 24.78;

percent H, 2.90; percent N, 21.87.

Calculated Lead Block Value: 119 T.N.T.=100.

Calculated Ballistic Mortar Value: 128 T.N.T.=100.

EXAMPLE III Preparation of MN dim'tro N,N*-bis(3,3,3-trinitropropyl)-2-butyne dicarbamate 0.5 gm. ofN,N'-bis(3,3,3-trinitropropyl)-2-butyne dicarbamate was dissolved in 10ml. acetic anhydride. While maintaining the temperature at about 5l0 C.,

the solution was added to 10 ml. 100% nitric acid and stirred for 20minutes: The solution was then poured over ice. The resulting whiteprecipitate was washed with water and recrystallized from "chloroform in60% yield, M.P. 115-1l6-C.- The elemental analysis of the product is, asfollows:

As a matter of convenience, the reaction is usually conducted in thepresence of an alkanoic anhydride.

The dicarbamates useful as starting materials are readily prepared bythe addition reaction of nitro isocyanates with nitro dio'ls, asdisclosed in my copending application Serial No. 479,655, filed January3, 1955, and with alkynyl diols, as disclosed in my copendingapplication Serial No. 479,656, filed January 3, 1955. p

. To more clearly illustrate my invention, the following examples arepresented. It should be understood, however, that these examples arepresented merely as a means of illustration and are not intended tolimit the scope of the invention in any way.

EXAMPLE I Preparation propyl)-2,2-dinitropropylene dicarbamateCalculated for C H N O percent C, 18.97; percent H, 1.74; percent N,24.14. Found: percent C, 19.29; percent H, 2.00; percent N, 24.21.

Calculated Heat of Combustion: 1784 1834 cal/gm.

Calculated Lead Block Value: 164 T.N.T.=l00.

Calculated Ballistic Mortar Value: 132 T.N.T.=l00.

EXAMPLE II Preparation of N,N-dinitro-N,N'-bis(3,3-dinitrobutyl)-2,2-dinitr0propylene dicarbamate While maintaining the temperature at0-5 C., 10 ml. of

Calculated for C H NmO percent C, 23.38; percent CalculatedLead BlockValue:'"137 'T.N.T."="100. l i

H, 1.96; percent N, 22.73. Found: percent C, 23.61; percent H, 2.19;percent N, 22.60.

Calculated Ballistic Mortar Value: 134 T.N.T.=100.

"The reaction is preferably run at temperaturesin the range of fromabout 0 to15" C. The reaction can be performed at higher temperature;however, it is preferred nitropropylene dicarbamate,N,N-'dinitr0-N,N-bis(3;3- dinitrohexyl)-2,2-dinitropropylenedicarbamate, N,N'-di'- nitro N,N bis(2,2,4,4 tetranitropentyl)2,2-dinitropropylene dicarbamate,N,N'-dinitro-N,N'-bis(3,3,3-trinitropropyD-B-hexyne dicarbamate,N,N'-dinitro-N,N'-

(3,3- dinitrobutyl)-2-butyne dicarbamate, gand N,N'-di-:

nitro-N-3,3-dinitrobutyl-N'-3,3,3-trinitropropyl butyne dicarbamate areprepared by reacting nitric acid respectively with:N,N'-bis(3,3,3-trinitropropyl)-2-nitropropyl- 9 ene dicarbamate,N,N-bis,(3,3-dinitrohexyl)-2,2-dinitro The resulting white precipitatewas cal/gm. Found: v

propylene dicarbamate, N,N' bis(2,2,4,4 tetranitro-Spentyl)-2,2-dinitropropylene dicarbamate, N,N-bis 3,3,3-trinitropropyl)-3-hexyne' dicarbamate, N,N-bis(3,3-dinitrobutyl)2-butyne;dicarbamate, and N,-3,3-dinitrobutyl- N-3,3,3-trinitropropylbutyne dicarbamate.

It is apparent that any member of the disclosed series ofN,N'-dinitro1dicarbama,tes can be prepared by merely reacting anappropriate dicarbamate with nitric. acid, ac cording to the teachingsof this invention. a

The nitro compounds of this invention are useful as high explosives andcan he used in any conventional explosive missile, projectile, rocket,sive charge. An example of such a missile is disclosed in United StatesPatent No. 2,470,162, issued May 17, 1949. One way of .usingthe highexplosives of this invention in a device such as thatdisclosed in UnitedStates Patent No. 2,470,162, is to pack the crystalline explosive inpowder form into the warhead of the missile. Alternatively, the crystalscan be first pelletiz'ed and then packed. charge thus prepared issutficiently insensi Patented Apr. 4, 1961 or the like, as the mainexplo- ".13 tive to withstand the shock entailed in the ejection of awhich comprises reacting nitric acid with a dicarbamate having thegeneral formula:

shell from a gun barrel or from a rocket launching tube under thepressure developed from ignition of a propel- H O lant charge, and canbe caused to explode. on operation I ll of an impactor timefuse-mechanism firing a detonating explosive such as lead azide ormercury fulminate.

I claim:

1. As compositions of matter, N,N-din itro dicarbamates having thegeneral formula:

i i R--NC-O-AOCNR' wherein R and R are lower nitroalkyl radicals and Ais a radical selected from the group consisting of lower nitroalkyleneand lower alkynylene radicals.

10. The method of claim 9 wherein the reaction is conducted in analkanoic anhydride media.

fi 1 I 10 11. The method of preparing N,N'-dinitro dicarbamates havingthe general formula: wherein R and R are lower nitroalkyl radicals and Ais N02 0 0 No,

a radical selected from the group consisting of lower 1 H I mtroalkylenel w qlkylencradlc'jflsj which comprises reacting nitric acid with adicarbamatc 2. As compositions of matter, N,N, d1ltf0 dicarbamhaving thegeneral formula.

ates having the general formula 0 Y if H i R1 s- -0A-o )-1 \*n'R-N-o0A;-0-CNRf wherein R and R are lower nitroalkyl radicals and A iswherein R and R are lower nitroalkyl radicals and A is lowerflitl'oalkylene radical. a lower nitroalkylene radical. 7' i 12. Themethod of preparing N,N-dinitro dicarbam- 3. As compositions of matter,N,N-dinitro dicarbamates having the general formula: ates having thegeneral formula: N0 0 0 NO:

NO: 0 0 R-L I C -OxKO-gnR' which comprises reacting nitric acid with adicarbamate wherein R and R are lower nitroalkyl radicals and A ishaving the general formula:

a lower alltylene radical. E I

4. As a composition of matter, N,N'-dinitro-N,N'- RNCO-AO-CN-R'bis(3,3,3 trinitropropyl)-2,2-dinitropropylene dicarharm wherein R and Rare lower nitroalkyl radicals and A is ate having the structuralformula; a lower alkynylene radical.

(3,3,3 trinitropropyl)-2,2-dinitropropylene dicarbamate 40 whichcomprises reacting nitric acid with N,N'bis(3,3,3-

5. As a composition of matter, N',N'-dinitro-N,N'- bis(3,3-dinitrobutyl)2,2 dinitropropylene dicarbamate having the structural formula:

trinitropro yl)-2,2-dinitropropylene dicaroamate.

6-. As a composition of matter, N,N'-dinitro-N,N

14. The method of preparing N,N'-dinitro-N',N-bisbis(3,3,3-trinitropropyl)-2-butyne discarbamate having the structuralformula;

7. As a composition of matter, N,N'-dinitro-N,N-biscomprises reactingnitric acid with N,N-bis(3,34iini-(3,3,3-trinitropropyl)-2-nitropropylene dicarbamatehavtrobutyl)-2,2-dinitropropylene dicarbamate. ing the structuralformula: 15. The method of preparing N,N'-dinitro-N,N-bis-3,3,3-trinitropropyl)-2-butyne dicarbamate which comprises reactingnitric acid with N,N-bis(3,3,3-trinitropropyl)-2-butyne dicarbamate.

8. As a composition of matter, N,N'-dinitro-N,N' bis-(3,3-dinitrohexyl)-2,2-dinitropropylene dicarbamate having thestructural formula:

16. The method ofpreparing i-I,i-I'-dinitro-N,N-bis-(3,3,3-trinitropropyl)-2-nitropropylene dicarbamate which 0 NO,comprises reacting nitric acid withN,N-bis(3,3,3-trinitropropyl)-2-nitropropylene dicarbamate. he m hod. psp riaa N N'r init gzNflf-bis 9. The method of preparing N,N'-dinitrodicarbarnatcs having the genera lformula:

(3,3-dinitrobuty1)-2,2-dinitropropylene dicarbamate which 5(3,3-dinitrohexyl) 2,2 dinitropropylene dicarbamate which comprisesreacting nitric acid With N,N'-bis(3,3- dinitrohexyl)-2,2-dinitropropylene dicarbamate.

18. The method of preparing N,N'-dinitro d-icarbamates having thegeneral formula:

wherein R and R are lower nitroalkyl radicals and A is References Citedin the file of this patent Curry et aL: I. Am. Chem. Soc. 73, 5043-6(1951). Gaylord: I. of Organic Chemistry 20, 546-548 (1955).

1. AS COMPOSITIONS OF MATTER, N,N''-DINITRO DICARBAMATES HAVING THEGENERAL FORMULA: